Month: December 2022

Taylor, Edward C. published the artcilePteridines. 47. Preparation and chemistry of 2-amino-6-carbalkoxy-3-cyano-5-substituted pyrazine 1-oxides: synthesis of pterin-6-carboxaldehyde, HPLC of Formula: 5098-14-6, the publication is Journal of Organic Chemistry (1980), 45(12), 2485-9, database is CAplus.

A new procedure for the synthesis of 2-amino-3-cyano-5-substituted pyrazines I [R = CH(OMe)₂, Me], useful intermediates for the synthesis of pteridines, is described. Oximation of β-oxo esters followed by reaction with aminomalononitrile provides 2-amino-6-carbalkoxy-3-cyano-5-substituted pyrazine 1-oxides II. Protection of the amino group as its (dimethylamino)methylenamino derivative I followed by S_N2 decarbalkoxylation provides pyrazines, which on removal of the protecting group and deoxygenation give pyrazines III. This method is designed to be of use in cases where the β-oxo ester cannot be converted directly to the corresponding α-oxo aldoxime. The procedure is applied to the synthesis of III [R = CH(OMe)₂], an intermediate in the synthesis of pterin-6-carboxaldehyde.

Journal of Organic Chemistry published new progress about 5098-14-6. 5098-14-6 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Salt,Sulfonic acid,Amine,Benzene, name is 2-Aminomalononitrile 4-methylbenzenesulfonate, and the molecular formula is C5H8N2O, HPLC of Formula: 5098-14-6.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Taylor, Edward C. published the artcilePteridines. 48. Utilization of 3,3-dimethoxy-2-pyrrolidinopropene for the synthesis of folic acid, N²‘-acetyl-7-folic acid, and 5-deaza-7-folic acid, Recommanded Product: 2-Aminomalononitrile 4-methylbenzenesulfonate, the publication is Journal of Organic Chemistry (1981), 46(7), 1394-402, database is CAplus.

Pyrrolidinopropene I was treated with NOCl and hydrolyzed to give (MeO)₂CHCOCH:NOH which was treated with NCCH(NH₂)CN to give II, a known precursor for III (R = CHO, R¹ = H). Treating I with 4-MeC₆H₄SO₃N:C(CN)₂ and then with NH₄OH gave IV [R² = H, R³ = (MeO)₂CH] which gave III (R = H, R¹ = CHO) (V) by guanidine cyclization. VI (R⁴ = CHO, R⁵ = H, X = CH) was prepared by treating I with MeOCH:C(CN)₂ followed by cyclizing with NH₄OH to give VII which was treated with HN:C(NH₂)₂, NaOH, and then HCl. Refluxing V with Ac₂O followed by condensation with 4-H₂NC₆H₄COGlu(OCMe₃)OCMe₃ gave VI (R⁴ = CH:NC₆H₄CO-Glu(OCMe₃)OCMe₃-4, R⁵ = Ac, X = N] which was reduced by NaBH₄ to give 37% VI (R⁴ = CH₂NHC₆H₄CO-Glu(OCMe₃)OCMe₃-4]. Similarly refluxing VI (R⁴ = CHO, R⁵ = H, X = CH) with 4-H₂NC₆H₄CO-Glu(OMe)OMe followed by reduction by NaBH₄ gave ∼40% VI [R⁴ = CH₂NHC₆H₄CO-Glu(OMe)OMe-4].

Journal of Organic Chemistry published new progress about 5098-14-6. 5098-14-6 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Salt,Sulfonic acid,Amine,Benzene, name is 2-Aminomalononitrile 4-methylbenzenesulfonate, and the molecular formula is C8H8O3, Recommanded Product: 2-Aminomalononitrile 4-methylbenzenesulfonate.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Ji, Xiaoyun published the artcileHighly regioselective aminobromination of α,β-unsaturated nitro compounds with benzyl carbamate/N-bromosuccinimide as nitrogen/bromine source, Category: nitriles-buliding-blocks, the publication is RSC Advances (2012), 2(13), 5565-5570, database is CAplus.

Aminobromination of α,β-unsaturated nitro compounds with benzyl carbamate and N-bromosuccinimide as nitrogen/bromine sources was reported. This new catalytic system tolerates a wide range of aromatic substrates, as well as heterocyclic and aliphatic substrates, resulting in good chem. yields. The reaction also proceeds smoothly with water as a medium in high efficiency. This practical aminobromination method was also suitable for large-scale preparation Furthermore, the N-carbobenzoxy protecting group could be easily cleaved to afford the free vicinal haloamines.

RSC Advances published new progress about 5153-73-1. 5153-73-1 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Alkenyl,Nitro Compound,Benzene, name is (E)-4-(2-Nitrovinyl)benzonitrile, and the molecular formula is C9H6N2O2, Category: nitriles-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Zhang, Jin-Jiang published the artcileTransition-metal free C-C bond cleavage/borylation of cycloketone oxime esters, HPLC of Formula: 238088-16-9, the publication is Chemical Science (2019), 10(1), 161-166, database is CAplus and MEDLINE.

An efficient transition-metal free C-C bond cleavage/borylation of cycloketone oxime esters has been described. In this reaction, the tetrahydroxydiborane (B₂(OH)₄) reagent not only served as the boron source but also acted as an electron donor source through formation of a complex with a N,N-dimethylacetamide (DMAc)-like Lewis base. This complex could be used as an efficient single electron reductant in other ring-opening transformations of cycloketone oxime esters. Free-radical trapping, radical-clock, and DFT calculations all suggest a radical pathway for this transformation.

Chemical Science published new progress about 238088-16-9. 238088-16-9 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Boronic acid and ester,Aliphatic cyclic hydrocarbon,Boronic Acids,Boronate Esters, name is 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)butanenitrile, and the molecular formula is C9H9BrO2, HPLC of Formula: 238088-16-9.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Zheng, Tucai published the artcileSynthesis and characterization of o-aryloxymethylbenzonitriles, Quality Control of 612-13-5, the publication is Xiandai Huagong (2010), 30(7), 35-37, database is CAplus.

Six o-aryloxymethylbenzonitriles are synthesized from o-cyanobenzyl chloride, phenol and substituted phenols and anhydrous potassium carbonate in N, N-dimethylformamide solvent via Williamson reactions. The yields of all six compounds are over 98%, and among them five compounds have not been previously reported. The products are characterized.

Xiandai Huagong published new progress about 612-13-5. 612-13-5 belongs to nitriles-buliding-blocks, auxiliary class Organic Pigment, name is 2-(Chloromethyl)benzonitrile, and the molecular formula is C4H4N2O2, Quality Control of 612-13-5.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Khomenko, Dmytro M. published the artcileSynthesis of α-substituted 2-(1H-1,2,4-triazol-3-yl)acetates and 5-amino-2,4-dihydro-3H-pyrazol-3-ones via the Pinner strategy, Application In Synthesis of 30431-99-3, the publication is Tetrahedron Letters (2021), 152956, database is CAplus and MEDLINE.

A series of 2-(1H-1,2,4-triazol-3-yl)acetates, as well as 4-mono- and 4,4-disubstituted 5-amino-2,4-dihydro-3H-pyrazol-3-ones (including spirocyclic derivatives) I [R¹ = H, i-Pr, Me; R² = H, Me; R¹R² = -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₂O(CH₂)₂-] have been synthesized using the Pinner reaction strategy. α-Mono- and α,α-disubstituted Et cyanoacetates NCC(R¹)(R²)C(O)OEt were converted into the corresponding carboxyimidate salts EtOC(=NH)C(R¹)(R²)C(O)OEt.HCl that served as the key intermediates. Their further reaction with formylhydrazide or hydrazine hydrate provided triazolylacetates I or aminopyrazolones (including spirocyclic derivatives) II, depending on the structure of the starting Pinner salt and the nature of the nucleophile. The scope and limitations of the developed synthetic method have been established.

Tetrahedron Letters published new progress about 30431-99-3. 30431-99-3 belongs to nitriles-buliding-blocks, auxiliary class Tetrahydropyran,Nitrile,Ester, name is Ethyl 4-cyanotetrahydro-2H-pyran-4-carboxylate, and the molecular formula is C9H13NO3, Application In Synthesis of 30431-99-3.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Costentin, Cyrille published the artcilePassage from stepwise to concerted dissociative electron transfer through modulation of electronic states coupling, Product Details of C8H6ClN, the publication is Chemistry – A European Journal (2009), 15(3), 785-792, database is CAplus and MEDLINE.

Reductive cleavage of the three cyanobenzyl chloride isomers in N,N-dimethylformamide gives new insights into the factors that control the mechanism during dissociative electron transfer. Within the family of investigated compounds, electrochem. reduction leads to expulsion of the chloride ion. While electron transfer is concerted with breaking of the C-Cl bond and acts as the rate-determining step in the case of both the ortho and para isomers, an intermediate anion radical is formed before rapid fragmentation in the case of the meta isomer. Such an unexpected mechanistic shift (all key thermodn. parameters are very similar for the three chlorides) is interpreted in the framework of a modified version of the dissociative electron-transfer model that includes electronic coupling effects between the diabatic states of the products. These effects appear to control the very existence of a transient species along the reaction pathway.

Chemistry – A European Journal published new progress about 612-13-5. 612-13-5 belongs to nitriles-buliding-blocks, auxiliary class Organic Pigment, name is 2-(Chloromethyl)benzonitrile, and the molecular formula is C8H6ClN, Product Details of C8H6ClN.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Wehman, Petra published the artcileLigand Effects in the Palladium-Catalyzed Reductive Carbonylation of Nitrobenzene, Application of Tetrakis(acetonitrile)palladium(II) Ditriflate, the publication is Organometallics (1994), 13(12), 4856-69, database is CAplus.

Reductive carbonylation of nitrobenzene in methanol in the presence of a palladium catalyst yields mainly Me N-phenylcarbamate. Diphenylurea is formed as the most important byproduct. A series of 4,4′-disubstituted-2,2′-bipyridyl ligands (R = F₃C, Cl, H, Me, MeO, and Me₂N) has been used to study the influence of the donating capacity of the ligand on the catalytic activity and selectivity. By way of two different types of complexes, Pd(ligand)₂(OTf)₂ and Pd(ligand)Cl(OTf), the influence of the anions in the catalytic system has also been studied. Electron-withdrawing substituents on the bipyridyl ligand turned out to completely deactivate the catalyst, while few differences were found between the ligands with electron-donating substituents. Chloride anions showed an inhibiting effect. The presence of water reduced the selectivity toward carbamate. At prolonged reaction times the urea side product was catalytically converted into the desired carbamate. Under more severe conditions carbamates, urea side products, and anilines were found with methoxy substituents on their Ph rings. X-ray structures were elucidated for Pd(bpy)₂(OTf)₂ and Pd(Mebpy)₂(OTf)₂. The Pd(bpy)₂(OTf)₂ crystals were monoclinic, space group P2₁/n, a = 8.0186(8) Å, b = 28.459(4) Å, c = 11.315(3) Å, β = 97.59(3)°, Z = 8, and final R = 0.046 for 3194 observed reflections. The Pd(Me-bpy)₂(OTf)₂ crystals were triclinic, space group P1, a = 11.726(6) Å, b = 11.870(3) Å, c = 13.871(2) Å, α = 103.63(6)°, β = 107.78(2)°, γ = 113.32(3)°, Z = 2, and final R = 0.147 for 5462 observed reflections. The CF₃SO₃^– moieties were not stable during refinement.

Organometallics published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C3H6F3N, Application of Tetrakis(acetonitrile)palladium(II) Ditriflate.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Cramer, Friedrich published the artcileOcclusion compounds. XVI. Stereospecific reactions with inclusion compounds, HPLC of Formula: 13312-84-0, the publication is Chemische Berichte (1959), 1739-47, database is CAplus.

cf. C.A. 53, 11245h. The following asym. reactions could be carried out with aqueous cyclodextrins (I): (1) asym. conversion of an easily racemizable atropisomeric 4,2-Me(p-MeC₆H₄SO₂)C₆H₃NAcMe (II); (2) synthesis of optically active mandelonitriles; (3) asym. partial oxidation of substituted benzoins; (4) partial saponification of racemic esters to optically active acids. The effect of the I depended on the ratio of the size of the I cavity to the geometric size of the included mol. The analogies to the mode of action of enzymes were discussed. β-I (1.00 g.) in 100 cc. H₂O treated with 0.03 g. II in 60 cc. Et₂O, shaken 7 hrs. at 25°, the Et₂O layer dried briefly, evaporated at 20°, and the residue (0.215 g.) dissolved in CHCl₃ and the rotation measured gave the following values of [α]²⁵_D at the time intervals in hrs. indicated in parentheses: -0.136° (0.33), -0.068° (0.67), -0.007° (15), -0.272° (0) (extrapolated). A similar run with 3.5 hrs. reaction time gave the following values: -0.125° (0.33), -0.063° (0.67), 0.0° (20), -0.250° (0) (extrapolated). α-I (2.0 g.) in 100 cc. pH 9 glycine buffer treated with 2 cc. o-ClC₆H₄CHO then dropwise with 2 g. liquid HCN, stirred 5 hrs. at 22°, extracted with 60 cc. Et₂O, and the Et₂O extract evaporated gave 2.316 g. o-ClC₆H₄CH(OH)CN (III), [α]²⁵_D 0.19° (EtOAc). α-I (1.5 g.) and 2.0 g. powd. p-ClC₆H₄CHO treated in the same manner with 2 g. HCN and stirred 2 hrs. at 22° yielded the p-isomer of III, [α]²⁵_D 0.21° (EtOAc); a portion in 10 cc. concentrated HCl kept 10 min. and worked up gave p-ClC₆H₄CH(OH)CO₂H, [α]²⁵_D -0.37° (EtOAc). 2,2′-Dichlorobenzoin (IV) (2.80 g.) and 1.0 g. α-I in 100 cc. pH 10 glycine buffer shaken 71 hrs. at 25° under O and extracted with 80 cc. Et₂O gave a solution of IV and active (o-ClC₆H₄CO)₂ (V), [α]²⁵_D 0.42; since only 50% active V was present in the oxidation product, the rotation was [α]²⁵_D 0.84°. 4,4′-Dichlorobenzoin (VI) gave similarly during 172 hrs. a solution of 50% VI and 50% (p-ClC₆H₄CO)₂ (VII), [α]²⁵_D 0.32° (EtOAc); pure VII had [α]²⁵_D 0.64°. β-I (1.5 g.) in 100 cc. pH 9 buffer treated with 1 cc. o-ClC₆H₄CH(OH)CO₂Et (VIII), b₁₃ 158-60°, stirred 2.5 hrs. at 58°, basified with 6 cc. 2N NaOH, extracted with EtOAc to isolate the unreacted VIII, the aqueous layer acidified with 25 cc. 4N H₂SO₄, extracted with EtOAc, and the extract evaporated in vacuo at 50° yielded 0.546 g. o-ClC₆H₄CH(OH)CO₂H, [α]²⁵_D 1.19° (EtOAc),and 0.480 g. VlII, [α]²⁵_D -0.73° (EtOAc). PhCHClCO₂Et (IX) (1 cc.), b₁₂ 128-30°, saponified similarly during 3.25 hrs. gave 0.395 g. PhCHClCO₂H, [α]²⁵_D 0.39° (EtOAc), and 0.633 g. IX, [α]²⁵_D -0.20° (EtOH). p-Isomer (X) of VIII (1.35 g.), b₁₆ 167-8°, m. 60-1°, saponified during 2.25 hrs. in pH 9 buffer at 60° yielded 0.417 g. p-ClC₆H⁴CH(OH)CO₂H, [α]²⁵_D 0.38° (EtOAc), and 0.893 g. X, [α]²⁵_D -0.17° (EtOAc). A similar run but at pH 10 and 22° during 6.5 hrs. yielded 0.622 g. acid, [α]²⁵_D 0.16° (EtOAc), and 0.509 g. X, [α]²⁵_D -0.29° (EtOAc). PhCH(OH)CO₂Et(XI) with β-I, and VIII and X with α-I under the same conditions did not yield optically active material. The rates of the ester hydrolyses at constant pH were measured for the following esters (pH, reaction temperature, rates of saponification with 1.32 mmoles β-I and with 1.32 mmoles α-I relative to the rate without I = 1.00, and diameter of ester in A. given): IX, 9.0 ± 0.2, 65°, 1.38, 0.94, 6.7; PhCHBrCO₂Et (b₁₃ 146-8°), 9.0 ± 0.2, 65°, 1.37, 1.01, 6.7; XI, 9.0 ± 0.2, 25°, 1.00, 1.00, 6.2; VIII, 8.0 ± 0.1, 65°, 0.77, 0.94, 8.2; X, 8.0 ± 0.1, 65°, 1.38, 1.05, 6.2.

Chemische Berichte published new progress about 13312-84-0. 13312-84-0 belongs to nitriles-buliding-blocks, auxiliary class Chloride,Nitrile,Benzene,Alcohol,Benzene Compounds, name is 2-(2-Chlorophenyl)-2-hydroxyacetonitrile, and the molecular formula is C8H6ClNO, HPLC of Formula: 13312-84-0.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Becart, Diane published the artcileHelical Oligourea Foldamers as Powerful Hydrogen Bonding Catalysts for Enantioselective C-C Bond-Forming Reactions, Category: nitriles-buliding-blocks, the publication is Journal of the American Chemical Society (2017), 139(36), 12524-12532, database is CAplus and MEDLINE.

Substantial progress has been made toward the development of metal-free catalysts of enantioselective transformations, yet the discovery of organic catalysts effective at low catalyst loadings remains a major challenge. Here we report a novel synergistic catalyst combination system consisting of a peptide-inspired chiral helical (thio)urea oligomer and a simple tertiary amine that is able to promote the Michael reaction between enolizable carbonyl compounds and nitroolefins with excellent enantioselectivities at exceptionally low (1/10,000) chiral catalyst/substrate molar ratios. In addition to high selectivity, which correlates strongly with helix folding, the system we report here is also highly amenable to optimization, as each of its components can be fine-tuned sep. to increase reaction rates and/or selectivities. The predictability of the foldamer secondary structure coupled to the high level of control over the primary sequence results in a system with significant potential for future catalyst design.

Journal of the American Chemical Society published new progress about 5153-73-1. 5153-73-1 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Alkenyl,Nitro Compound,Benzene, name is (E)-4-(2-Nitrovinyl)benzonitrile, and the molecular formula is C9H6N2O2, Category: nitriles-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts